Improved antifouling properties of polyamide nanofiltration membranes by reducing the density of surface carboxyl groups.

Carboxyls are inherent functional groups of thin-film composite polyamide nanofiltration (NF) membranes, which may play a role in membrane performance and fouling. Their surface presence is attributed to incomplete reaction of acyl chloride monomers during the membrane active layer synthesis by interfacial polymerization. In order to unravel the effect of carboxyl group density on organic fouling, NF membranes were fabricated by reacting piperazine (PIP) with either isophthaloyl chloride (IPC) or the more commonly used trimesoyl chloride (TMC). Fouling experiments were conducted with alginate as a model hydrophilic organic foulant in a solution, simulating the composition of municipal secondary effluent. Improved antifouling properties were observed for the IPC membrane, which exhibited lower flux decline (40%) and significantly greater fouling reversibility or cleaning efficiency (74%) than the TMC membrane (51% flux decline and 40% cleaning efficiency). Surface characterization revealed that there was a substantial difference in the density of surface carboxyl groups between the IPC and TMC membranes, while other surface properties were comparable. The role of carboxyl groups was elucidated by measurements of foulant-surface intermolecular forces by atomic force microscopy, which showed lower adhesion forces and rupture distances for the IPC membrane compared to TMC membranes in the presence of calcium ions in solution. Our results demonstrated that a decrease in surface carboxyl group density of polyamide membranes fabricated with IPC monomers can prevent calcium bridging with alginate and, thus, improve membrane antifouling properties.

Ultrafiltration membranes incorporating amphiphilic comb copolymer additives prevent irreversible adhesion of bacteria.

We examined the resistance to bacterial adhesion of a novel polyacrylonitrile (PAN) ultrafiltration membrane incorporating the amphiphilic comb copolymer additive, polyacrylonitrile-graft-polyethylene oxide (PAN-g-PEO). The adhesion of bacteria (E. coli K12) and the reversibility of adhered bacteria were tested with the novel membrane, and the behavior was compared to a commercial PAN ultrafiltration membrane. Under static (no flow) bacterial adhesion tests, we observed no bacterial adhesion to the PAN/PAN-g-PEO membrane at all ionic strengths tested, even with the addition of calcium ions. In contrast, significant adhesion of bacterial cells was observed on the commercial PAN membrane, with increased cell adhesion at higher ionic strengths and in the presence of calcium ions. Under crossflow filtration conditions, initial bacterial deposition rate increased with ionic strength and with addition of calcium ions for both membranes, with generally lower bacterial deposition rate with the PAN/PAN-g-PEO membrane. However, deposited bacteria were readily removed (between 97 and 100%) from the surface of the PAN/PAN-g-PEO membrane upon increasing the crossflow and eliminating the permeate flow (i.e., no applied transmembrane pressure), suggesting reversible adhesion of bacteria. In contrast, bacterial adhesion on the commercial PAN membrane was irreversible, with approximately 50% removal of adhered bacteria at moderate ionic strengths (10 and 30 mM) and less than 25% removal at high ionic strength (100 mM). The resistance to bacterial adhesion of the PAN/PAN-g-PEO membrane was further analyzed via measurement of interaction forces with atomic force microscopy (AFM). No adhesion forces were detected between a carboxylated colloid probe and the PAN/PAN-g-PEO membrane, while the probe exhibited strong adhesion to the commercial PAN membrane, consistent with the bacterial adhesion tests. The exceptional resistance of the PAN/PAN-g-PEO membrane to bacterial adhesion is attributable to steric repulsion imparted by the dense brush layer of polyethylene oxide (PEO) chains.